Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/41—Preparation of salts of carboxylic acids
  • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/22—Tin compounds
  • C07F7/2224—Compounds having one or more tin-oxygen linkages

Definitions

• the invention generally relates to tin-(IV)-carboxylates and is particularly directed to a method for the preparation of anhydrous tin-(IV)-carboxylate.
• tin-(II)-acetate A method for the preparation of tin-(II)-acetate is disclosed in the literature.
• Gmelin, 8th Ed., 1975, No. 46, Part C 2, pp. 220-221 discloses the reaction of metallic tin and glacial acetic acid wherein the reaction is permitted to proceed for 80 to 90 hours under reflux conditions and in an inert gas atmosphere.
• Tin-(II)-acetate is the sole reaction product, but no tin-(IV)-acetate is formed.
• tin-(IV)-acetate In order to produce tin-(IV)-acetate, expensive intermediate compounds first have to be prepared such as, for example, thallium acetate. The thallium acetate is reacted in acetic acid anhydride with tin-(IV)-iodide or tin-(IV)-bromide to obtain tin-(IV)-acetate. This procedure is exceedingly cumbersome and, from an economics point of view, requires substantial expenditure.
• anhydrous tin-(IV)-carboxylate is prepared in a two-stage process wherein, in the first stage, tin-(IV)-acetate is prepared which, in the second stage, is transferred into the desired carboxylate by being reesterified with the corresponding acid anhydrides or carboxylic acids.
• metallic tin or Sn-(II)-acetate is treated with an excess of acetic acid anhydride, the reaction mixture being stirred and heated to temperatures of 50° to 150° C. while passing oxygen through the mixture or by adding an oxygen yielding agent.
• the tin-(IV)-acetate thus obtained is separated and then reacted in known manner with carboxylic acids with more than four carbon atoms or the corresponding organic acid anhydrides at a temperature of 80° to 150° C.
• the liberated acetic acid anhydride or acetic acid is then removed by distillation under vacuum conditions.
• the metallic tin in order to increase its reactivity, is preferably used in the form of a fine powder.
• the reaction of the metallic tin or of the Sn-(II)-acetate takes place at 50° to 150° C.
• the preferred temperature range is 80° to 130° C. It has been found to be advantageous to carry out the reaction in the presence of acetic acid as solvent.
• the oxidation of the tin into the four-valent stage is carried out with oxygen or oxygen yielding agents.
• an aqueous hydrogen peroxide solution As oxygen yielding agent, it is advantageous to use an aqueous hydrogen peroxide solution.
• the reaction mixture is cooled after a reaction period of 5 to 8 hours and the precipitated tin-(IV)-acetate is removed by filtration and dried.
• the white anhydrous tin-(IV)-acetate precipitates in a yield of 70 to 80%.
• additional tin-(IV)-acetate can be recovered so that the total yield can be increased to about 97%.
• the second method stage comprises the reaction of the anydrous tin-(IV)-acetate, obtained in the first stage, with carboxylic acids with more than four carbon atoms or the corresponding organic acid anhydrides at temperatures of 80° to 150° C. while, at the same time, distilling off the liberated acetic acid anhydride or acetic acid. The removal by distillation is accomplished at reduced pressure. In this manner, the corresponding tin-(IV)-carboxylates are obtained in simple manner in anhydrous form.
• the reaction of tin-(IV)-acetate with the organic acid anhydride or the organic acid is performed at temperatures of 100° to 110° C. under slight vacuum conditions.
• the tin-(IV)-carboxylate corresponding to the organic acid anhydride used is obtained in this manner in substantially quantitive manner.
• Organic acid anhydrides of carboxylic acids with more than four carbon atoms to be used pursuant to the invention are, among others, propionic acid anhydride, butyric acid anhydride and valeric acid anhydride.
• Particularly preferred are the anhydrides of the higher molecular fatty acids such as, for example, of lauric acid, palmitic acid or stearic acid.
• carboxylic acids with more than four carbon atoms valeric acid, caprylic acid or undecanoic acid are suitable.
• the higher molecular acids such as myristic acid, palmitic acid or steric acid are preferably used.
• unsaturated fatty acids are the oleic acid and the linoleic acid.
• fatty acids with up to 22 carbon atoms or their anhydrides are preferred.
• the anhydrous tin-(IV)-acetate obtained in the first stage of the inventive method can be used as the tin basis compound in the application of electrically conductive and infrared reflecting layers on glass and ceramic surfaces.
• the tin-(IV)-acetate, as such, or in suitable formulations is useful for chemical preservation of glass surfaces.
• these are suitable as gliding and lubricating agents as well as agents facilitating the compression of sintered materials, particularly on the basis of bronze.
• Another field of application for tin-(IV)-acetate is the production of tin-containing metal oxane compounds.
• the yield is 103.7 gram anhydrous tin-(IV)-acetate.
• This experiment was also carried out in a 500 ml, four-neck flask fitted with thermometer, cooler, stirrer and gas introduction pipe.
• the yield is 52 gram anhydrous tin-(IV)-acetate.
• the separated tin-(IV)-acetate is also removed by filtration and, together with the first filtrate amount, is washed three times with about 75 ml of butyl acetate.
• the washed tin-(IV)-acetate is subsequently dried at room temperature in vacuum at 2 mm Hg in a rotation evaporator.
• the yield is 227.6 gram anhydrous tin-(IV)-acetate.
• the experiment was carried out in a 1 liter four-neck flask fitted with thermometer, cooler, stirrer and gas introduction pipe.
• the yield is 65.4 gram anhydrous tin-(IV)-acetate.
• the acetic acid which is formed is removed by distillation under vacuum conditions (20 to 2 mm Hg/100° C.) and is received in cooling traps. The acetic acid has been quantitatively distilled off in about 6.5 hours.
• the yield is 124.8 gram tin-(IV)-stearate.
• acetic acid anhydride is subsequently removed by distillation under vacuum conditions (20 to 2 mm Hg/100° C.) and is received in cooling traps. Substantially the entire amount of acetic acid anhydride is distilled off in about 6.5 hours.
• the yield is 127.0 gram tin-(IV)-stearate.
• acetic acid is removed by distillation under vacuum conditions at about 20 to 2 mm Hg/100° C. and is received in cooling traps (distillation time, about 6 hours). The acetic acid has been quantitatively distilled off in about 6 hours.
• the yield is 96.2 gram tin-(IV)-montanate.
• the yield is 57.0 gram tin-(IV)-caproate.

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• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)

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• 1990
  • 1990-02-06 DE DE4003488A patent/DE4003488A1/de not_active Withdrawn
• 1991
  • 1991-01-24 EP EP91100864A patent/EP0441183B1/fr not_active Expired - Lifetime
  • 1991-01-24 DE DE91100864T patent/DE59100539D1/de not_active Expired - Fee Related
  • 1991-01-29 US US07/647,403 patent/US5068373A/en not_active Expired - Fee Related

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